JPH02282249A - Processing solution for silver halide photosensitive material, silver halide photosensitive material and processing method - Google Patents

Abstract

PURPOSE:To accelerate the processing of a photosensitive material by adding a specified heterocyclic compd. (salt) to a processing soln. CONSTITUTION:A 3- or 4-membered heterocyclic compd. (A) capable of being adsorbed on silver halide or a salt of the compd. A is added to a processing soln. for a silver halide photosensitive material, preferably a processing soln. having a fixing ability. A compd. represented by formula I, II or III may be used as the compd. A. In the formulae I-III, each of Z1-Z3 is a group of atoms required to form a desired ring and each of M1 and M2 is H or a counter cation. A compd. represented by formular IV is a concrete example of the compd. represented by the formula I, II or III. The compd. A may be incorporated into the photosensitive material.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a processing solution for silver halide light-sensitive materials, a silver halide light-sensitive material, and a processing method for the same, and in particular, it relates to a processing solution for silver halide light-sensitive materials, and a method for processing the same. The present invention relates to processing solutions, silver halide photosensitive materials, and processing methods.

(Prior Art) With progress in the field of electronics, rapid processing is also required in the field of silver halide photosensitive materials.

In particular, in the development process of sheet-like photosensitive materials such as graphic arts photosensitive materials, X-ray photosensitive materials, photosensitive materials for scanners, and photosensitive materials for CRT image recording,
The need for rapid processing is increasing.

Another advantage of rapid processing is that the tank capacity required to develop a unit amount of photosensitive material per unit time is smaller, meaning that the automatic processor can be smaller. The significance is great.

However, as development processing speeds up, there are problems such as sensitizing dyes contained in silver halide light-sensitive materials not being completely eluted during processing and leaving behind color in the light-sensitive materials (so-called residual color). Deterioration of photographic performance due to delayed desorption of dyes from silver halide (suppression of development, suppression of fixation,
This increases the problem of bleaching inhibition, etc.

Conventionally, as a method to reduce residual color, research disclosure magazine (几search Disclosure)
(1) A water-soluble stilbene compound, a nonionic surfactant, or a mixture of both is added to the developer solution, as described in RE) Volume 107, A-207jJ (/lPJ'/year, July issue). (2) treating the photographic element after development, bleaching, and constant N with an oxidizing agent to destroy the dye; and (3) converting the bleach bath into a persulfuric acid preservation bath. However, these methods are insufficient when there is a large amount of residual color, do not actively promote the desorption and dissolution process of the sensitizing dye, and are not particularly suitable for rapid processing.

(Objective of the Invention) Therefore, the object of the present invention is firstly to provide a processing solution for rapidly processing silver halide photosensitive materials, and secondly to provide a silver halide photosensitive material suitable for rapid processing. The third objective is to provide a method for processing silver halide light-sensitive materials that allows rapid processing, and the fourth objective is to solve the problem of residual color of sensitizing dyes and deterioration of photographic performance in rapid processing. Our goal is to provide the following.

(Structure of the Invention) The object of the present invention is to provide a processing solution for a silver halide photosensitive material containing at least one tricyclic or tetracyclic heterocyclic compound or a salt thereof that can be adsorbed to silver halide; satisfying the following condition 1; and can be adsorbed to silver halide 3
or a silver halide photosensitive material containing at least one type of tetracyclic heterocyclic compound or its salt; and 3 which satisfies the following condition 1 and can be adsorbed to silver halide.
Alternatively, it has been achieved by a method for processing a silver halide photosensitive material, which is characterized by processing an exposed silver halide photosensitive material in the presence of at least one tetracyclic heterocyclic compound or a salt thereof.

Condition 1: Anhydro 5,5'-dichloro-9-ethyl 3.3"
- Mix two 4oxio-' mol/β aqueous solutions of bis(3-sulfopropyl)thiacarbocyanine hydroxide pyridinium salt with 1 ml of potassium chloride 1°0×10-' mol/β aqueous solution, and add to this mixture. Furthermore, the compound 8.0
Add 4 ml of ×10-” mol/l aqueous solution and dilute with water to
Adjust the volume to 0d.

The molecular extinction coefficient of this aqueous solution at 624 nm is 1.0.
×105 or less.

The tri- or tetracyclic heterocyclic compound that can be adsorbed on the silver halide used in the present invention is a compound in which at least one ring-constituting atom is an oxygen atom, a sulfur atom, a nitrogen atom, a selenium atom, or a tellurium atom. The molecular weight of the compound is preferably 600 or less, more preferably 500 or less.

It is also preferably water soluble, with water 1 at 20'C.
Compounds that can dissolve 0.04 g or more, particularly 0.08 g or more per 00H are preferred.

Preferred tri- or tetracyclic heterocyclic compounds that can be adsorbed on silver halide are the following general formula (I):
It is a compound represented by general formula (II) or general formula (I).

Among these compounds, compounds that satisfy Condition 1 above are preferred.

(The following is a blank space) General formula (1) In the formula, the atomic group necessary to form Z1μ3 or ≠ layered heterocycle is represented. M□ represents a hydrogen atom or a counter cation.

-8M□ in general formula (1) is desirably bonded to the carbon atom of Z□.

Z□ may have a substituent.

Examples of tri- or ≠ layered heterocycles formed by zo include saturated or unsaturated virole ring, imidazole ring, triazole ring, thiadiazole ring, tetrazole ring, thiazole ring, isothiazole ring, pyrazole ring, oxazole ring, and inoxazole. ring, selenazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, triazine ring, quinoxaline ring, tetraazaindene ring, oxadiazole ring) sennadiazole ring, indazole ring, triazaindene ring, tetrazole ring, indole ring, indole ring Indole ring, indolenine ring, chromene ring, chroman ring, quinoline ring, isoquinoline ring, quinolidine ring, cinnoline ring, phthalazine ring, quinazoline ring, nateridi/ring, purine ring, pteridine ring, indolizine ring, furan ring, Thiophene ring, pyran ring, azepine ring, oxazine ring, thiazepine ring, carbazole ring, xanthine ring, phenanthridine ring, acridine ring, perimidine ring, phenanthroline ring, thianthrene ring, phenoxathiine ring, phenoxazine ring, phenothiazine ring, Preferably, the ring is a tricyclic or polycyclic heterocycle selected from a phenazine ring, a benzene ring, a naphthalene ring, an anthracene ring, etc., or formed by condensation with each other.

Ml may be an alkali metal (e.g. sodium, potassium, etc.) or an organic base (e.g. triethylamine,
Pyridine, DBU (/, r-diazabicyclo [j, Hiroshi,
Examples include counter cations such as conjugate acids such as 0]-7-undecene), and hydrogen atoms may also be tuffed.

General formula (II) In the formula, Z2 has the same meaning as 2□. However, structures in which the thioxo group can be cyenolized by tautomerism are excluded.

In the formula, =S is preferably bonded to 22 carbon atoms.

General formula (I[I) Of the tri- or ≠ layered heterocyclic compound formed by Z3ViZ process, all the atomic groups necessary to form a compound capable of forming iminosilver are removed.

M2 is synonymous with Ml.

In the present invention, those having a petero ring as shown below are particularly preferred.

In addition, these polycyclic compounds may have a substituent, and preferred substituents include a rhodan atom,
-0M (M is a hydrogen atom or a monovalent metal (e.g. Na,
,KXLi)y,%Was. ), substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amine group, niano group, nitro group, sulfo group, carboxyl group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted acyl group, substituted or unsubstituted aminosulfonyl group, substituted or unsubstituted alkoxy Examples include a carbonyl group, a substituted or unsubstituted allyloxycarbonyl group, and a substituted or unsubstituted aminocarbonyl group.

In particular, the alkyl group preferably has a carbon number of JO or less; for example, a methyl group, an ethyl group, a -1-hydroxyethyl group, a -1-diethylaminoethyl group, a propyl group, an inpropyl group, a 3-dimethylaminopropyl group, and a methyl group. , isopentyl group, hexyl group, cyclohexyl group, heptyl group, hensyl group, octadecyl group, etc. The aryl group preferably has 7j or less carbon atoms, and examples thereof include %J, t-haphenyl group, 1-, 1-ru group, sulfophenyl group, carboxyphenyl group, naphthyl group, and sulfonaphthyl group. The alkoxy group preferably has 20 or less carbon atoms, and includes, for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, an octadecyloxy group, and the like. The substituted amino group preferably has 20 or less carbon atoms, such as dimethylamino group, diethylamino group, hydroxyamino group, -1hydrokinethylamino group, -1sulfoethylamino group, -1diethylaminoethylamino group, Examples include anilino group and β-naphthylamino group. The aryloxy group preferably has 20 or less carbon atoms, and ff1J, t
Examples include haphenoxy group, gooselphophenoxy group, and β-naphthyloxy group. The alkylthio group preferably has 20 or less carbon atoms, such as methylthio group, ethelthio group, -2-hydroxyethylthio group, codietheramineethylthio group, dodecylthio group, cosulfoethylthio group, 3-sulfopropylthio group. group, Gnulfobutylthio group, and the like. The arylthio group preferably has a carbon number of 20 or less, and includes, for example, a phenylthio group, a β-naphthylthio group, a gousulfophenylthio group, and the like. The acyl group preferably has 20 or less carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butyryl group, a stearoyl group, and a benzoyl group. The number of carbon atoms for the substituted amine sulfonyl group,
Those having a molecular weight of 20 or less are preferable, and examples thereof include a diethylaminonulfonyl group, a di(,2-hydroxyethyl)aminosulfonyl group, an anilinosulfonyl group, a -1nulphethylaminocarbonyl group, and a dodecylaminosulfonyl group. The alkoxycarbonyl group preferably has carbon atoms or less, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a methoxyethoxycarbonyl group, a diethylaminoethoxycarbonyl group, and a benzyloxycarbonyl group. The aryloxycarbonyl group preferably has 20 or less carbon atoms, such as a phenoxycarbonyl group, a Hiro-sulfophenyloxycarbonyl group, and a tolyloxycarbonyl group. The substituted aminocarbonyl group preferably has a carbon number of JO or less, and includes a diethylaminocarbonyl group, a diethylaminocarbonyl group, a propylaminocarbonyl group,
Octadecylaminocarbonyl group! -Flufoethylaminocarbonyl group and the like.

Further, the polycyclic compound may be in the form of an inorganic or organic acid salt. Preferred examples of inorganic or organic acids include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. can be lost.

All specific examples of the compounds of the present invention are shown below, but the present invention is not limited to these compounds.

(,2) [gu] (?) (j) (ri) H (,<) (/θ)] (//) (/,2) (/l) (CH2)3S03Na (/3) (/≠) (CH2) 3 b Os Na (/3) When all the molecular extinction coefficients at t2≠m of the aqueous solutions obtained according to the procedure for all the compounds shown in these specific examples/ are measured, both O and Si The molecular weight of all compounds is also 100 or less.

The compounds of the present invention may also be described, for example, in ``Heterocyclic Compounds - Thiazoles and Their Derivatives'', edited by Metzger, John Wiley & Sons (1997) (Metzger).

“Heterocyclic Compounds -
Tbiazoleand Its Derivati
ves'', John Wiley & So mouth S (,
17), John Castle, “Heterocyclic Compounds Condensed Pyridazines Containing Cinoline and Phthalazine”, John Castle.

Willie and Sons C/yy 3rd year) (Cast
le,”Heterocyclic Compound
s-Condensed Pyridazines I
ncluding C1nnolines and P
hthalazines, John Wiley
& 5ons (1973)) and “Comprehensive Heterocyclic Chemistry Volume 6” edited by Bocc.
, Pergamon Press (1984) (Potts,
”Comprehensive Heter.

cycletc chemistry vol, 6',
Pergamon PreSs (1984)), JP-A-53-44596, U.S. Patent No. 3,904.41
No. 2, Journal of India Chemical Husiety 5, Vol. 53, p. 420 (1976) (J, In
dian Chem, 5oc53, 420 (19
It can be easily synthesized by the method described in 76)).

The compounds of the present invention function to enable rapid processing of silver halide light-sensitive materials. In particular, it functions to extremely reduce the amount of sensitizing dye remaining in photographic materials after processing.

In the present invention, the above-mentioned compound may be added to the silver halide photosensitive material or to a processing solution for processing the silver halide photosensitive material.

When added to a silver halide photosensitive material, the photosensitive emulsion layer, non-photosensitive layer (intermediate layer, protective layer, henk layer provided on the opposite side of the support from the side on which the silver halide emulsion layer is provided)
It may be added to any layer such as. The amount added is 0.0001 to 100 mol% of the total amount of coated silver, preferably 0.0
001-50 mol%, particularly preferably 0.0001-2
It is 0 mol%.

A particularly preferred embodiment of the present invention is one in which the compound of the present invention is added to the treatment solution.

The photographic processing of the present invention consists of at least the steps of developing, fixing, washing (or stabilizing), and drying the exposed silver halide photosensitive material in the case of a black and white photosensitive material, and the steps of drying the exposed silver halide photosensitive material in the case of a color photosensitive material. The exposed photosensitive material is at least
Color development, bleaching, fixing (bleaching and fixing may be carried out in the same bath, i.e. bleach-fixing bath), washing with water (or stabilization)
, consists of a drying process.

The compound of the present invention may be added to any of the developer solution, color developer solution, fixer solution, bleach solution, bleach-fix solution, washing solution (or stabilization solution), or a prebath thereof. In particular, it is preferable to add it to a processing solution containing fat. Calories added to the treatment solution are 5 x 10''5 to 10 mol/β, preferably 10-
'~5X10-2 mol/l, special Q mol or 3 X
If the amount is less than the range of 10-'' to 10-2 to 10-2 mol/min, no effect of improving the suitability for 6-speed processing can be obtained, and if it exceeds this range, precipitation may occur in the processing solution or increase the cost.

As a developing agent for use in black-and-white photographic processing, it is preferable to use a developer mainly containing dihydroquinones, since it is easy to obtain good performance. In addition, 1-phenyl-3-pyrazolidones, p-aminophenols, and the like may be used as auxiliary developing agents.

Examples of dihydroxyhenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 23-dichlorohydroquinone, 2.5-dichlorohydroquinone, 23-dibromohydroquinone, and 25-dimethylhydroquinone, but especially hydroquinone. is preferred.

As a p-amine phenolic developing agent, N-methyl-p
-aminophenol, p-aminophenol, N-(β
-hydroxyethyl)-p-aminophenol, N-(
4-hydroxyphenyl)chrysin, 2-methyl-p-
There are aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

3'' As a pyrazolidone developing agent, 1-phenyl-
3-pyrazolidone, 1-phenyl-4,4-dimethyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4
, 4-dihydroxymethyl-3-pyrazolidone, ■-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1
-p-tolyl-4,4-dimethyl-3-pyrazolidone,
1-p-1 lylu-4-methyl-4-hydroxymethyl-
3-pyrazolidone, etc.

The developing agent is preferably used in a concentration of usually 0.01 mol/I to 1.2 mol/I.

Preservatives for sulfite include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. Sulfite is 0.2 mol/f! The above is especially 0. 4 mol/
1 or more is preferable. Further, the upper limit is preferably 2.5 mol/l.

The pH of the developer is preferably in the range of 9 to 13. More preferably, the pH range is from 10 to 12.

Alkaline agents used to set pH include pPI regulators such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

Patent Application No. 61-28708 (Borate), JP-A-Sho G.O.
Buffers such as No.-93433 (eg, sucrose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc. may be used.

Further, a hardening agent may be used in the developer. As the hardening agent, a dialdehyde hardening agent or its bisulfite adduct is preferably used, and specific examples thereof include glutaraldehyde and its bisulfite adduct.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol = mercapto such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may contain antifoggants such as indazole compounds such as 5-nitroindazole, benztriazole compounds such as 5-methylbenztriazole, etc.
Disclosure Volume 176, No. I 764
3. Development accelerators described in Section XXI (December issue, 1978) and, if necessary, toning agents, surfactants, antifoaming agents, water softeners, and those described in JP-A-56-106244. It may also contain amino compounds and the like.

In the development process, a silver stain preventive agent, such as the compound described in JP-A-56-24347, can be used in the developer.

The developer is European Ii'i-Permit No. 0136582.
Amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, by F.A. Mason [Photographic Processing Chemistry J, published by Focal Press (
(1966), pp. 226-229, U.S. Patent No. 2. ,
193. Those described in No. 01.5, No. 2,592°364, and JP-A-48-64933 may also be used.

The fixer is an aqueous solution containing thiosulfate as a fixing agent;
It has a pH of 3.8 or more, preferably 4.2 to 7.0.

More preferably one is 84.5 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, but ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be varied as appropriate, and is generally about 0.1 to about 6 mol/1.

The fixer may also contain water-soluble aluminum-rum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potash alum, and the like.

In the fixing solution, tartaric acid, citric acid, gluconic acid, or their derivatives can be used alone or in combination of two or more. These compounds are 0.0 per fixer 11
Those containing 0.05 mol or more are effective, especially 0.01 mol/l
~0.03 mol/1 is particularly effective.

The fixing solution may optionally contain preservatives (e.g. sulfites, bisulfites), pH buffers (e.g. acetic acid, boric acid), pH adjusters (e.g. sulfuric acid), chelating agents with water softening ability, and patent applications. The compound described in No. 60-218562 may be included.

The swelling percentage of the photosensitive material is reduced (preferably 150
% to 50%) Treatment dura can be weakened or quickly treated, which is more preferable. It is more preferable that there is no hardening film during Zunawaji development, and even more preferable that there is no hardening film during fixing, or the pH of the fixing solution may be set to 4.6 or higher to weaken the hardening reaction. By doing this, it is possible to configure a replenisher consisting of one solution each for the developer and the fixer.
The advantage also arises that the preparation of the replenisher requires only dilution with water.

The silver halide photographic material of the present invention is treated with washing water or a stabilizing solution after the development and fixing steps.

Here, the stabilizing liquid is the same as washing with water, only the name is different.

The amount of replenishment of washing water or stabilizing liquid is 2 per m' of light-sensitive material.
f! The following (including O, that is, washing with water) is preferable.

By doing so, it is possible not only to save water, but also to eliminate the need for piping for installing the automatic processor.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multistage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done.

To make the above development process water-saving or piping-free,
It is preferable to apply anti-mildew means to the washing water or the stabilizing liquid.

As anti-mildew methods, the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the ion exchange resin described in JP-A No. 61-1'31632 are used. A method of purifying water by using
-253807, 60-295894, 61-
Methods using antibacterial agents described in No. 63030 and Il-51396 can be used.

Furthermore, L, E, West, 'l'/aLer Qu
ality Cr1teria"PhoLo, Sci,
& Eng, Vol. 9 No. 6 (1965),
M.W.

[1each, Microbiological G
rows in Mo eyes OnPicLure Pr
ocessing'' SMPTIE Journal
Vol, 85, (1976), R,0,Dee
gan,”PhotoOPprocessingtVasb
Water Biocides” J, Imagi
ng Tech l 01No.

6 (1984) and JP-A No. 5'l-8542, No. 57
-58143, 58-105145, 57-1
No. 321.46, No. 58-18631, No. 5'l-9
Antibacterial agents, antifungal agents, surfactants, etc. described in No. 7530, No. 5.7-157244, etc. can also be used in combination.

Additionally, R, T, Kreim
an, J, 1mage, Tecb 10, (6)2
Isothiazoline compounds described on page 42 (1984), Re5earch Disclosure No. 5ea
Isothiazoline compounds described in rchDisclosure 981, May issue), Volume 228-1 No.
, 22845 (April 1983) 1
' Sochi-7zoline compounds, compounds described in Japanese Patent Application No. 1987-51396, etc. are used as antibacterial agents (Microbioci
It can also be used in combination as de).

In addition, "Chemistry of anti-bacterial and anti-mildew" by Hiroshi Horiguchi, published by Sankyo Publishing (1973).
7), "Handbook of Antibacterial and Antifungal Technology", Japanese Society of Antibacterial and Antifungal Research, Hakuhodo (1988) may also be included.

When the silver halide photographic light-sensitive material of the present invention is washed with a small amount of washing water or stabilized with a stabilizing liquid,
1. It is more preferable to provide a septic tank with six squeeze rollers as described in No. 163217.

Further, it is also preferable to employ a water washing step configuration as disclosed in Japanese Patent Application No. 61-290619.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water depending on the treatment, is disclosed in Japanese Patent Application Laid-open No. 60-2.
As described in No. 35133, it can also be used in a processing liquid having fixing ability, which is a processing step before that.

In the case of a black and white light-sensitive material, the silver halide light-sensitive material of the present invention, when processed with an automatic processor that includes at least the steps of development 1, fixing, water washing or stabilization and drying, processes from development to drying. The process must be completed within 90 seconds, that is, from the time when the leading edge of the photosensitive material begins to be filled with the developer until it is dried through the fixing, washing (or stabilization) steps, and the leading edge exits the drying zone. time (so-called Dr.
yL.

Dry time) is preferably within 90 seconds, particularly preferably within 70 seconds. More preferably, this Dry
jo Dry time is within 60 seconds.

In the present invention, "developing process time" or "developing time" refers to the time from when the leading edge of the photosensitive material to be processed as described above is immersed in the developing tack solution of an automatic processor until it is immersed in the next fixing solution; "Fixing time J" is the time from immersion in the fixing tank liquid until immersion in the next washing tank liquid (stabilizing liquid). "Washing time" refers to the time during which the film is immersed in the washing tank liquid.

In addition, "drying time J" means that the drying zone where hot air of 35°C to 100°C, preferably 40°C to 80°C is blown, is This refers to the time you are in the zone.

In order to achieve the above-mentioned dry-to-dry rapid processing within 90 seconds, the development time is within 30 seconds, preferably within 25 seconds, and the development temperature is 25°C to 51'C, preferably 30°C. ~・40°C is more preferable.

In the present invention, the fixing temperature and time range from about 20°C to about 50°C.
6 seconds to 30 seconds at °C is preferred, and 6 seconds to 20 seconds at 30 °C to 40 °C is more preferred.

The water washing or stabilization bath efficiency and time are preferably 6 seconds to 20 seconds at 0 to 50°C.1. , <, more preferably 6 seconds to 15 seconds at 1.5°C to 40°C.

In the present invention, the developed, fixed and washed or stabilized photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying is approximately 40°C to approximately 1000°C
The drying time is suitably changed depending on the surrounding conditions, but it is usually about 5 seconds to 30 seconds, and particularly preferably about 1 second to 20 fdy17 at 40°C to 80°C.
-Yes.

Sensitive material of the present invention
When performing dry development for 90 seconds or less, in order to prevent uneven development peculiar to rapid processing, Japanese Patent Application No. 61-297
A roller made of rubber material as described in the specification of No. 672 is applied to the roller at the outlet of the developing tank.
In particular, as described in the specification of Sho 61-297673, the discharge flow rate for stirring the developing solution in the developer tank should be set to 1/min or more, and further, the patent application Sho 61-297673 may 6
1. As described in Japanese Patent Application No. 31.5537, it is more preferable to increase the fixing speed and to use opposed rollers for at least the development process, especially for the rollers in the fixer tank. By using opposed rollers, the number of rollers can be reduced and the processing tank can be made smaller. In other words, it is possible to make the automatic processor more compact.

The photographic sensitizer of the present invention is not particularly limited and can be used for general photosensitive materials. For example, photographic materials for laser printers for medical images, scanner sensitive materials for printing, medical direct imaging X-ray imaging materials, medical indirect imaging X-ray imaging materials,
It can be used for CRT image recording photosensitive materials, high contrast photosensitive materials for printing, color negative photosensitive materials, color reversal photosensitive materials, color photographic paper, etc.

The above photosensitive material of the present invention can be produced by, for example, one of the following methods or a combination of two methods.

(2) Use silver halide containing little or no iodine. That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. with a silver iodide content of 0 to 5 mol % are used.

■ Adding a water-soluble iridium salt to the silver halide emulsion.

■ Reduce the amount of silver coated in the silver halide emulsion layer. For example, 1-5 g/m on one side, preferably 1-4
g/rr? shall be. More preferably 1 to 3 g/m'
It is.

■ Reduce the average grain size of silver halide in the emulsion. For example, it is 1.0μ or less, preferably 0.7μ or less.

(2) Tabular grains, such as those with an aspect ratio of 4 or more, preferably 5 or more, are used as silver halide grains in the emulsion.

-Reduce the swelling percentage of the X-rodanide photosensitive material to 200% or less.

Silver halide grains in photographic emulsions may be so-called regular grains having regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical shapes. grains, grains with crystal defects such as twin planes, tabular grains, or composites thereof.

It is given as the ratio between the average value and the average value of the grain thicknesses on the sides of the tabular grains. In the present invention, preferred grain forms in the case of tabular grains include aspect ratios of 4 or more and less than 20;
More preferably (7 or more and less than 10).Furthermore, the thickness of the grain is preferably 0.3μ or less, particularly preferably 0.2μ or less.
It is preferable that the amount is 90% or more, more preferably 90% or more.

The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution.

The silver halide photographic emulsion of the present invention can be produced by a known method, for example, by Re5earCh Disclosure.
No. 17643 (1, December 978), 22~
Page 23, “■, Emulsion preparation (Bmu[5ion prep
aration andl:ypes)' and same, N
o, 187] 6 (November 1979), p. 64.8.

The photographic emulsion used in the present invention is based on "The Chemistry and Physics of Photography" by Glafkide, published by 2Polmontel (P.
ides, Chimie eL Plysique
Photographique.

Paul Monsel, 1967), Duffin,
"Photographic Emulsion Chemistry", published by Focal Press (G, F,
Duffin.

Yen + ologographic Emulsior +
ChCmistry (Focal Press.

196='6), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, 2elik
nlan etal, Jal Yu+g, anci Co
atiB Photographic Emulsio
n.

Focal Press, 1964).

When forming the silver halide grains used in the present invention, in order to control the growth of the grains, ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat.
, No. 271,157, No. 3.574628, No. 3
, 704, No. 1.30, No. 4,297.439, No. 4,276.374, etc.), thione compounds (e.g., JP-A No. 54-14'4, No. 319, No. 53-82, 4
08, No. 5577.737, etc.), amine compounds (for example, JP-A-54-100,717, etc.), etc. can be used.

In the present invention, water-soluble rhodium salts and water-soluble iridium salts as described above can be used.

In the present invention, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method of keeping pΔg constant in the liquid phase in which silver halide is produced, that is, the so-called Chondrald double jet method, can be used. According to this method, the crystal form is regular and A silver halide emulsion with near uniform grain size is provided.

The silver halide emulsion used in the present invention is preferably chemically sensitized.

In the case of chemical sensitization, ordinary sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used.

More specific chemical sensitizers include sulfur sensitizers such as Allyl thiocarbamide, thiourea, thiosa sulfate, thioether and cystine; -1
-(Potassiumcl) 1oro Pa1lad
ate), reduction sensitizers such as tin chloride, phenylhydrazine, and reductone, and the like.

The silver halide emulsion of the present invention is spectrally sensitized using a known spectral sensitizing dye, if necessary. Spectral sensitizing dyes that can be used include, for example, Hamer, "Heterocyclic Compounders: Cyanine Soybeans and Related Compounders", John Wheeley and Sons (1964) (F. M. Tiam).
er, 'fleterocyclic Compoun
ds -The Cyanine Dyes
'and Related Compounds'',
John Wiley & 5ons (1964) and Starmer, “Heterocyclic Compounds – Special Topics in Heterocyclic Compounds”.
Chemistry, John Wiley & Sons (1977) (D.M., Sturmer.

Heterocyclic CompoundS
-5special Topics 1nHeter
cyclic Chemistry', John'W
Cyanine, merocyanine, logocyanine, styryl, hemicyanine, oxonol, benzylidene, holopolar, etc., which are described in Iley & 5ons (1977), etc. can be used; -75339, 62-6251, 59-21.2827, 50
Examples include cyanine dyes and merocyanine dyes represented by the general formulas described in No. 122928 and No. 59-1801553. Specifically, JP-A-60-1.33
No. 442, pages (8) to (11), JP-A-61-753
No. 39, pages (5) to (7), pages (24) to (25), JP-A-62-6251, pages 00)-(15), JP-A-59-212827, page ( Pages 5) to (7), pages (7) to (9) of JP-A No. 50-122928, pages (7) to (1) of JP-A-59-18055'3, etc. Examples include sensitizing dyes that spectrally sensitize silver halide in the blue region, fringe region, red region, or infrared region of the spectrum.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic ring group (e.g., U.S. Pat. Nos. 2,933,390 and 3,635°721)
(as described in US Pat. No. 3,743,510), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent Bundle 3°615.6], No. 3, 3,6
15.64], 3.617, 295, 3.6.
The combinations described in No. 35,721 are particularly useful.

The above sensitizing dye is 5 x 10-7 per mole of silver halide.
It is contained in the silver halide photographic emulsion in a proportion of -5X 10-2 moles, preferably 1xio-' moles to 1x10-3 moles, particularly preferably 2xio-' moles to 5X10-' moles.

The sensitizing dyes described above can be dispersed directly into the emulsion layer. They can also be first dissolved in a suitable solvent, such as methyl alcohol, ethyl alcohol, methyl cellochloride, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution overnight. can. Ultrasonic waves can also be used for dissolution. Also-
A method for adding the sensitizing dye described above is described in US Pat. No. 3. 4
69. 987, etc., a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion, Japanese Patent Publication No. 46-24185. A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 61-45217; A method of mechanically pulverizing and dispersing the emulsion in the emulsion and adding this dispersion to the emulsion;
A method of dissolving a dye in a surfactant and adding the solution to an emulsion as described in US Pat. A method of dissolving a compound using a compound and adding the solution to an emulsion; a method such as that described in JP-A-50-80826, in which a dye is dissolved in an acid substantially free of water, and the solution is added to an emulsion. methods etc. are used. Other additions to emulsions include U.S. Patent No. 2,912,34.3, U.S. Pat.
The method described in JP-A No. 3,429,835 and the like can also be used. The sensitizing dyes described above may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but of course the silver halide may be dispersed during any step of the preparation of the emulsion. can.

The above-mentioned sensitizing dyes may be used in combination with other sensitizing dyes. For example, US patent bundle 3°703.37
No. 7, No. 2,688,545, No. 3,397,0
No. 60, same No. 3. [i15. No. 635, same No. 3,
No. 628,964, British Patent No. 1.242,588;
Same 1st. ．． No. 293,862, Japanese Patent Publication No. 43-4936, No. 44-14030, No. 43-IO773, U.S. Patent No. 3,416.9. ．． No. 27, Special Publication Showa 43-4: J3
No. 0, U.S. Patent Bundle No. 2,615,613, U.S. Patent No. 3. 6
15. No. 632, No. 3.6'17,295, No. 3,635, . Sensitizing dyes described in No. 721 and the like can be used.

In order to rapidly process the silver halide photosensitive material, it is preferable that the swelling percentage of the silver halide photosensitive material is 200% or less.

On the other hand, if the swelling percentage is too low, the speed of development, fixing, water washing, etc. will be reduced, so it is not preferable to lower it more than necessary.

The preferred swelling percentage is 200% or less and 30% or more,
Particularly preferred is 150% or less and 50% or more.

A person skilled in the art can easily control the swelling percentage to 200% or less by, for example, increasing the amount of hardening agent used in the photosensitive material.

The swelling percentage was determined by (a) incubating the photographic material at 38°C and 150% relative humidity for 3 days, (b) measuring the thickness of the hydrophilic Coro-11 layer, and (C) measuring the thickness of the photographic material at 2.
Soak in 1 °C distilled water for 3 minutes, and fdl step (b)
It can be determined by measuring the percentage change in the layer thickness compared to the thickness of the hydrophilic colloid layer measured in .

Examples of hardening agents that can be used in the present invention include aldehyde compounds, compounds containing active halogens as described in U.S. Pat. No. 3,288,775, and U.S. Pat.
Compounds having a reactive ethylenically unsaturated group as described in U.S. Pat. No. 5,718, etc., epoxy compounds described in U.S. Pat.

Organic compounds such as genocarboxaldehyde are known. Among these, vinyl sulfone hardeners are preferred. Furthermore, polymer hardeners can also be preferably used.

As the polymer hardening agent, a polymer having an active vinyl group or a group that is a precursor thereof is preferable, and in particular, a long spacer as described in JP-A No. 56-142524 is used to form an active vinyl group or a precursor thereof. Particularly preferred are polymers in which the group is bonded to the polymer main chain. The amount of these hardeners added to achieve the above swelling percentage varies depending on the type of hardener used and the type of gelatin.

When rapidly processing the silver halide light-sensitive material of the present invention, it is preferable to contain an organic substance in the emulsion layer and/or other hydrophilic colloid layers that would flow out during the development process. When the substance to be discharged is gelatin, it is preferable to use a gelatin species that is not involved in the crosslinking reaction of gelatin by a hardening agent, such as acetylated gelatin or phthalated gelatin, and preferably has a small molecular weight. On the other hand, examples of polymeric substances other than gelatin include polyacrylamide as described in U.S. Pat. No. 3,271,158, polyvinyl alcohol,
Hydrophilic polymers such as polyvinylpyrrolidone can be effectively used, and saccharides such as dextran, saccharose, and pullulan are also effective. Among these, polyacrylamide and dextran are preferred, and polyacrylamide is a particularly preferred substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. In addition to this, Re5earch Disclosure 1st
Volume 76, No. 17643, Section ■ (December issue, 19
Antifoggants and stabilizers described in 1978) can be used.

The silver halide photosensitive material of the present invention is disclosed in U.S. Pat.
．． No. 401, No. 4,168,977, No. 4,16
6.742, same No. 4. 311. No. 781, No. 4
, No. 272,606, No. 4,221.857, No. 4,243,739, etc., silver halide that can obtain photographic characteristics with ultra-high contrast and high sensitivity using hydrazine derivatives. Can be applied to photosensitive materials.

The present invention can also be applied to silver halide color light-sensitive materials. The case of silver halide color light-sensitive materials will be described in detail below.

In the present invention, in the case of a color photographic material, the first
The term "process" refers to the first processing step, and in the processing of color negative films, this usually corresponds to the color developing solution.

The present invention is effective when the so-called wet processing time from when the photosensitive material is immersed in the processing solution in the first step until it is removed from the processing solution in the final step is 6 minutes or less, and is particularly effective for 5 minutes and 30 seconds. It is preferable that the duration is less than 5 minutes because the effect becomes more pronounced, and more preferably 5 minutes or less.

Among the wet processing times of 6 minutes or less, fixing or bleach-fixing times of 2 minutes or less are preferred, and more preferably 1 minute and 30 seconds or less from the viewpoint of clear effects. or,
The present invention is applied when the total replenishment amount of each processing solution is 2,500 or less per meter of color photographic light-sensitive material, particularly 2,500 or less.
000 ml or less is preferable, and 1800 ml or less is more preferable.

Above all, the effect of the present invention becomes more remarkable when the amount of replenishment of the fixing solution or bleach-fixing solution is 12°00ml. The following cases are preferred, and more preferably 8007 nl or less, particularly 600 gloss or less.

Further, it is more preferable that the replenishment amount of the color developer is 7007 nl or less, more preferably 500 d or less. In addition, it is more preferable that the amount of replenishment of the bleaching solution is 600 d or less, more preferably 300 d or less.

In addition, when the present invention is applied to a color photographic light-sensitive material, the effect is remarkable on a color photographic light-sensitive material for photographing using a silver iodobromide emulsion, especially when the total thickness of all photographic constituent layers excluding the support is 20 μm or less. and exhibits superior effects in color photographic light-sensitive materials in which the film swelling rate TH of the binder in the photographic emulsion layer is 10 seconds or less, and furthermore, the film swelling rate Ty2 is 8 when the thickness of all the photographic constituent layers is 18 μm or less. It is preferable that the time is less than a second.

Here, the photographic constituent layers refer to all the hydrophilic colloid layers that are on the same side as the support surface that has the silver halide emulsion layer and are involved in image formation, and in addition to the silver halide emulsion layer,
For example, it includes an antihalation layer (black colloidal silver antihalation layer, etc.), a subbing layer, an intermediate layer (simple intermediate layer, a filter layer, an ultraviolet absorbing layer, etc.), a protective layer, and the like.

The thickness of the photographic constituent layer is the total thickness of the above hydrophilic colloid layers, and is measured using a micrometer.

In the silver halide color photographic light-sensitive material of the present invention, the binder film swelling rate T% of the silver emulsion layer is 25 seconds or less. That is, the hydrophilic binder used for coating silver halide in silver halide color photographic light-sensitive materials is usually gelatin, but a high molecular weight polymer may also be used. is T
'A must be 25 seconds or less. The swelling rate TIA of the binder can be measured according to any method known in the art, such as the knee-green (Δ
, Photographic Science and Engineering (Photo, Sci) et al.
.

Eng.), Vol. 19, No. 2, pp. 124-129. /2 is a color developer at 30°C for 13 minutes and 15 minutes.
The maximum swollen film thickness of 90% reached when the film is processed for seconds is defined as the saturated film thickness, and is defined as the time required to reach the film thickness A.

That is, the time T'A until the film thickness reaches the saturated film thickness due to swelling is defined as the film swelling rate.

The membrane swelling rate T''A can be adjusted by adding a hardening agent to gelatin as binder.

Hardening agents include aldehyde-based, aziridine-based (for example, PB Report 19,921, U.S. Patent 2.950,1
No. 97, No. 2,964,404, No. 2,983,61
No. 1, No. 3,271,175, Special Publication No. 46-4089
No. 8, JP-A No. 50-91315, etc.), isoxazolium systems (e.g., U.S. Pat. No. 3,321,3)
No. 23), epoxy systems (such as those described in U.S. Pat.
04j, No. 394, West German Patent No. 1,085,663, British Patent No. 1,033,518, Japanese Patent Publication No. 1973-35495
etc.), vinyl sulfone type (for example, P
B report 19,920, West German patent 1,100,942
No. 2,337. '412, same 2. ,545,72
No. 2, No. 2,635゜518, No. 2,742,308
No. 2,749.260, British Patent No. 1,251,0
No. 91, U.S. Patent No. 3,539,644, U.S. Patent No. 3,490
No. 911, etc.), acryloyl (for example, those described in U.S. Pat. No. 3,640,720), carbodiimide (for example, U.S. Pat. Nos. 2,938,892 and 4,043,818) , No. 4.061,499,
those described in Japanese Patent Publication No. 46-38715, etc.), triazine type (for example, West German Patent No. 2,410,973, West German Patent No. 2.
553. No. 915, US Pat. No. 3,325,287, Japanese Patent Application Laid-Open No. 52-12722, etc.), polymer type (for example, British Patent No. 822,061, US Patent No. 3.
No. 623,878, No. 3,396,029, No. 3,2
No. 26,234, Special Publication No. 47-18578, No. 185
79, No. 47-48896, etc.), maleimide-based, acetylene-based, methanesulfonic acid ester-based, and N-metrol-based hardening agents can be used alone or in combination. Useful combination techniques include, for example, West German Patent Nos. 2,447,587 and 2. ．． 505,74
No. 6, No. 2,514,245, U.S. Patent No. 4,047.
No. 957, No. 3,832,181, No. 3゜840.3
No. 70, JP-A-48-43319, JP-A No. 50-6306
No. 2, No. 52-127329, Special Publication No. 48-3236
Examples include combinations described in No. 4 and the like.

The following are examples of processing steps to which the present invention is applied.

1. Color development - Bleach fixing - Washing 21 Color development - Bleach fixed - Washing - Stable 3. Color development -
Bleach - Bleach-fix - Wash - Stable 4. Color development - Bleach-fix -
Stable 5, color development - constant bleaching - stable 6, color development - bleaching - constant bleaching - fixing - stable 7, color development constant - bleaching - fixing - washing - stable 8, color development constant - bleaching - fixing - stable 9, black and white development -Water washing, color development, reversal, adjustment, bleaching, fixing, washing, and stabilization.Next, details of the processing solution will be described.

The color developing agent used in the color developer and color developer replenisher is an aromatic primary amine compound, and includes known compounds that are widely used in various color photographic processes. However, in the present invention, the preferred color developing agent is (1,14-(N-ethyl-N-β)
-hydroxyethylamino)-2-methylaniline sulfate (2+4-(N-ethyl-N-β-methanesulfonamidoethylamino)-2-methylaniline sulfate (3) 4-(N-ethyl-N-β -methoxyethylamino)-2-methylaniline-p-1 luenesulfonate +4) 4-(N,N-diethylamino)-2-methylaniline hydrochloride (5) 4-(N-ethyl-N-dodecylamino )−・−
2-Methylaniline sulfate (6)' N,N-dialkyl-p-phenylenediamine-based color developing agent such as N,N-diethyl-p-phenylenediamine hydrochloride. These compounds are added to the color developing solution in an amount of 0.005-0.05 mol/p, preferably 0.01-0.04 mol/p, particularly preferably 0.015-0.04 mol/p. It is in the range of 0.03 mol/l. In addition, in the color development replenisher, it is preferable to add it to a higher concentration than the above concentration. Specifically, how high the concentration should be depends on the replenishment amount setting, but
1.05-2.0 times the color developing solution (mother solution), more often 1.0 times the color developer (mother solution). 2-1. It is added in an 8-fold range.

The above color developing agents may be used alone or in combination depending on the purpose. Examples of preferred combinations include (1) and (2), (1) and (
3), (2) and (3).

In the present invention, the bromide ion concentration of the color developer is 0.0.
For this purpose, it is preferable to keep the bromide content of the replenisher below 0.005 mol/l. Generally, the more the replenishment amount is reduced, the lower the bromide content in the replenisher should be set, and in particular in the present invention, it is preferable that the replenisher does not contain bromide in order to significantly reduce the replenishment amount. .

Note that examples of the bromide include potassium bromide, sodium bromide, lithium bromide, hydrobromic acid, and the like.

The color developer and color developer replenisher contain hydroxylua,
Preservatives such as amine, diethylhydroxylamine, triethanolamine, compounds described in West German patent (OLS) No. 2622950, hydrazines, sulfites, and bisulfites described in JP-A-63146041 are used. be done.

In addition, various chelating agents are also added for the purpose of water softening and metal hiding, but in the present invention, the following - formation (A
) and/or at least one of the compounds represented by (13)
Preferably, it contains seeds.

General formula (A) M2O,P-(,-PO,M.

○H In the formula, n represents 1 or 2, R represents a lower alkyl group, M may be the same or different, and represents a hydrogen atom, an alkali metal atom, or ammonium.

R is particularly preferably a methyl group or an ethyl group, and M is preferably a hydrogen atom or a sodium atom.

Specific examples of compounds represented by general formulas (A) and (B) are shown below.

(A-1) (A-2) (B-1) CH.

H+O+P CP 0zHz ○Ding 1 (B-2) C,H.

H2O5P-C-P○, H.

In addition to the above-mentioned compounds, the color developing solution used for H. , development inhibitors or antifoggants such as mercapto compounds; organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium, amines, thiocyanates; Nucleating agents: auxiliary developing agents such as l-phenyl-3-pyrazolidone; viscosity-imparting agents; also -forming (A), (B)
In addition to compounds represented by
Various chelating agents such as the organic phosphonic acids described in 1.) can be used alone or in combination.

In the present invention, the pH value of the color developer and its replenisher is usually 9 or more, preferably 9.5=12, particularly preferably 9.5-11.0.

In the above range, the replenisher for the color developer is
It is preferable to set the value to about 0.05-0.5 higher.

Further, the temperature in the color development process is 30-45°C, but a high temperature is preferable to achieve a low replenishment process, and in the present invention, the temperature is 35-45°C.
C1 It is particularly preferable to carry out the reaction at 38-42°C.

Although the present invention can be carried out using either an automatic processor or manual processing, it is preferable to carry out the process using an automatic processor. In the process of an automatic processor, a single color developer tank or multiple color developer tanks may be used, but replenishment can be further reduced by using multiple tanks and using a multi-stage forward replenishment system in which the first tank is refilled and the color developer is sequentially flowed into the rear tanks. be able to. In addition, the contact area between the developer and the air in the tank should be as small as possible.Specifically, a thick lid, a seal using a liquid with a high boiling point and a specific gravity lower than that of the developer, and JP-A-63- 21
The use of a shielding means such as a tank structure constricted to the opening described in No. 6050 further enhances the effectiveness of the present invention.

Further, as a means for enhancing the effects of the present invention, it is preferable to replenish water in accordance with the amount of evaporation in order to correct evaporation concentration of the developer. The water to be replenished is preferably deionized water that has undergone ion exchange treatment, or deionized water that has been treated with reverse osmosis, distillation, or the like.

The color developer and color developer replenisher are prepared by sequentially adding and dissolving the above-mentioned chemicals in a certain amount of water, and it is preferable to use the above-mentioned deionized water as the water for preparation.

In the present invention, the photosensitive material after color development is treated with a bleach solution or a bleach-fix solution. The bleaching agents used in these processes are generally complex salts of ferric ions and chelating agents such as aminopolycarboxylic acids, polycarboxylic acids, and aminopolycarboxylic acids. Examples of preferable chelating agents used as complex salts with these ferric ions include:
(1) Ethylenediaminetetraacetic acid (2) Diethylenetriaminepentaacetic acid (3) Cyclohexanediaminetetraacetic acid (4) 1,3-diaminopropanetetraacetic acid (5) Nitrilotriacetic acid (6) Iminoniacetic acid (7) Glycol ether diamine tetraacetic acid, etc. In particular, (1), (2), (3), (4)
) is preferable in terms of finishing performance and quickness of bleaching.

The ferric ion complex salt may be used in the form of a complex salt, or as a ferric ion complex salt.
Iron salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. and aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc. - A ferric ion complex salt may be formed in a solution using an agent. When used in the form of complex salts, 1
Different types of complex salts may be used, or two or more types of complex salts may be used. Examples of this are especially (1) and (4).
It is preferable to use the following agents in combination. On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used.

Furthermore, one type or two or more types of clearing agents may be used. In any case, the chelating agent may be used in excess of the amount needed to form the ferric ion complex. Among iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.1 to 1 mol 1, preferably 0.2 to 0.4 mol, in bleaching solutions for color photographic materials such as color negative films. mol/l, and in the bleach-fix solution 0.05 to 0.5 mol/-I! , preferably 0.1 to 0.3 mol/'l. Further, in a bleaching solution or a bleach-fixing solution for color photographic photosensitive materials for printing such as color paper, the amount is 0.03 to 0.3 mol/1, preferably 0.405 to 0.2 mol/l.

Further, a bleach accelerator may be used in the bleaching solution or bleach-fixing solution, if necessary. As specific examples of useful bleaching accelerators, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and are particularly preferred in US Pat. 893. No. 858, West German Patent No. 1,29
Compounds described in No. 0,812 and JP-A-53-95630 are preferred.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (
For example, a rehalogenating agent of potassium bromide, sulfur bromide, ammonium bromide) or chloride (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodide (e.g. ammonium iodide) can be included.

If necessary, one or more types having an r+ H buffering capacity such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The above bleaching solution is usually used in the range of r) I (3 to 7, preferably 3.5 to 6.5, particularly preferably 4.
It is 0 to 6.0. In addition, in the case of bleach-fix solution, l) 1
-14 to 9, preferably 5-.8, particularly preferably 5.5-7.5. If the pH is higher than the above range, defective bleaching tends to occur, and if it is lower, defective color development of the cyan dye is likely to occur.

The fixing agent used in the bleach-fixing solution of the present invention or the fixing solution used after processing with the bleaching solution is a known fixing agent, such as a thiosulfate such as sodium thiosulfate or ammonium thiosulfate, sodium thiocyanate, or ammonium thiocyanate. Thiocyanates such as: ethylene bisthioglycolic acid, thioether compounds such as 3,6-cythia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas; Can be used in combination of more than one species. Also, JP-A-51
A special bleach-fix solution made of a combination of a fixing agent described in Japanese Patent No. 155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of fixing agent per 11 moles is preferably 0.5 to 3 moles, particularly 1 to 2 moles in processing f7 color photographic photosensitive materials.
The amount ranges from 0.5 to 1 mole in the processing of color photographic materials for printing.

The pH range of the fixer in the present invention is preferably 4 to 9, particularly preferably 5 to 8. If it is lower than this, the liquid deteriorates significantly, and conversely, if p ]'-1 is higher than this, ammonia is likely to volatilize from the ammonium salt contained and staining is likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

The bleach-fix solution and fixer used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.], bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) It contains sulfite ion-releasing compounds such as sulfite ion-releasing compounds, aromatic sulfinic acids such as benzenesulfinic acid, para-toluenesulfinic acid, or salts thereof. The content of these compounds is preferably about 0.02 to 0.50 mol/j2, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

After the fixing process or bleach-fixing process, processing processes such as washing with water and stabilization are generally performed. Other processing methods may also be used.

Note that the water washing process removes processing liquid components that have adhered to or occluded in the color light-sensitive material, or unnecessary components in the color light-sensitive material] 7. This improves the image stability and film properties after processing. Has a protective effect.

On the other hand, a stabilization process is a process that achieves a level that cannot be achieved by washing with water. This is a process that improves the storage stability of images.

The washing process is sometimes carried out in one tank, or often in two tanks.
It is carried out using a multi-stage countercurrent water washing method over cypress wood.

The amount of water in the washing step can be set arbitrarily depending on the type of color photosensitive material and the purpose.For example:. journal·
of Motion Picture Ant Television
Engineering Vol. 64, pp. 248-253 (1955
“Water Flowrates in Immersion Washing of Motion Picture Film” (May issue)
rqersion-Washing of Motion
nPicture Film, S, R, Goldw
It can also be calculated by the method described in J. Asser. .

When reducing the amount of water used for washing, the growth of bacteria and mold becomes a problem.
It is preferable to use the washed water with reduced calcium and magnesium as described in the specification of No. 8. Also, fungicides and fungicides, such as Journal of Amp.
LΔn1il) act.

Anjifug, A7ants) vol, 1
], No, 5, p 2 o 7-22
3 (1,983) and the compounds described in "Chemistry of Germicidal and Antifungal" by Hiroshi Horiguchi) can be added. In addition, chelating agents such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid may be added as water softeners.

When reducing the amount of water used for washing, the amount of water used is usually 100 m per 1 m of color photosensitive material! -1500- is used, and a range of 200d to 800ml is particularly preferably used in terms of achieving both two-color image stability and water-saving effect.

The p I-1 in the water washing step is usually in the range of 5 to .9. Other various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, thorium hydroxide, aqueous ammonia, mono- (using combinations of carboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.), similar disinfectants that can be added to the washing water, disinfectants, formalin and formalin-releasing compounds such as hexamethylenetetramine, and others depending on the application. Fluorescent brighteners can be added, ammonium chloride, ammonium sulfite,
Various ammonium salts such as ammonium sulfate and ammonium thiosulfate can be added.

The pH of the stabilizing bath is usually 3 to 8, but depending on the type of sensitive material and the purpose of use, a low pH range of 3 to 5 may be particularly preferred.

The present invention can be applied to processing various color photosensitive materials. Color negative film for general use or movies,
Typical examples include color reversal films for slides or televisions.

Various color couplers can be used in the present invention, specific examples of which are listed in Research Disclosure (R.
D) It is described in the patent described in No. 17643, ■-〇-G. As dye-forming couplers, couplers that give the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development are important, and specific examples of diffusion-resistant, 4-equivalent or 2-equivalent couplers are given in the above-mentioned RD.
In addition to the couplers described in the patents No. 17643, Vll-C and No. 0, the following can be preferably used in the present invention:

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers that have a ballast group.

As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an annulamino group is preferable from the viewpoint of the hue of the coloring dye and the coloring density.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol couplers and phenol couplers, and representative examples include preferably oxygen atom-eliminating two-equivalent naphthol couplers. In addition, couplers that can form cyan dyes that are stable against humidity and separation are
Typical examples of preferred examples include phenolic cyan couplers having an alkyl group of ethyl or higher in the meta-position of the phenol nucleus, 2,5-diacylamino-substituted as described in U.S. Pat. No. 3,772.002. These include phenolic couplers, phenolic couplers having a phenylureido group at the 2-position and a sialamino group at the 5-position, and the 5-amidonaphthol cyan coupler described in European Patent No. 161626A.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
Examples of 5' magenta couplers are described in U.S. Pat. Specialty couplers may form dimers or higher polymers. Typical examples of polymerized dye-forming couplers are described in, for example, US Pat. No. 3,451,820.

Specific examples of polymerized magenta couplers are described in U.S. Pat.
, No. 367.282, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD'T7643;
The patented couplers described in sections (1) to (F) are useful.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds include British Patent Nos. 2,097°140, 2,131,
It is described in No. 188. Others, Japanese Patent Application Publication No. 60 (1983) = 18
DIR redox compound releasing couplers such as those described in European Patent No. 1.73,302A can be used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Pat. No. 2,322,02.
It is stated in issue 7 etc.

Further, the process and effects of the latex dispersion method, as well as specific examples of latex for impregnation, are described in U.S. Patent No. 4,199°363 and West German Patent Application No. It is described in '541°274 and '541,230.

Next, specific examples of the present invention will be shown, but the present invention is not limited thereto.

Example 1 Preparation of emulsion 30g of gelatin and 6g of potassium bromide were added to 1j2 of water.
Add silver nitrate aqueous solution (5g as silver nitrate) and iodizing power while stirring in a container kept at °C! An aqueous solution of potassium bromide containing 0.15 g of potassium bromide was added over 1 minute using the double di-knit method. Furthermore, silver nitrate water bath solution (as nitric acid starvation/4tJ)
An aqueous potassium bromide solution containing potassium iodide and 2Si'i was added by a double jet method. The addition flow rate at this time is
The trap flow rate was accelerated so that the flow rate at the end of addition was three times that at the start of cooperation 0.

3. After adding calories, use the sedimentation method. After all soluble salts were removed at s 0c, the temperature was raised to +o'C, all of the gelatin 732 was added, and the pH was adjusted to A, 7. The resulting emulsion has a projected area diameter of 0.7? The grains were tabular grains with an average dry thickness of 1 .mu.m and 3 r.mu.m, and a silver iodide content of 3 mol. This emulsion was chemically sensitized using gold and sulfur sensitization.

In the preparation of photographic forest materials, as a protective layer, in addition to gelatin, an average molecular weight r000
Polyacrylamide, polystyrene sulfonic acid, polymethyl methacrylate fine particles (average particle size 3)
．． A seratin aqueous solution containing 0 μm), polyethylene oxide, and a hardening agent was used.

Anhydro-J, 3'-monocycloterether-3,3'-di(3-sul7oprobyl)oxacarbocyanine hydroxide sodium salt i j OO■/1 mol Ag was added to the above emulsion as a sensitizing dye. Potassium iodide was added at a rate of 200 mq/1 mol Ag. Furthermore, a stabilizer (-teguhydroxy-t-methyl-/,!
, ,7a,7-chitrazainde/and,2. J
bis(hydroxyamino)-goodiethylamino-/,
3. ! -1-Ryazine and nitrone, Y/limethylolpropane as a drying antifoggant, a coating aid, and hardening agent 1 are added to form a coating solution, which is coated and dried on both sides of the polyethylene terephthalate support at the same time as the top protective layer. It was prepared by The amount of silver coated is 7m per side.
Met.

Preparation of developer kit: Part (A), Part) C13) and Part (C) below.
) A developer kit (concentrated solution) was prepared.

Part (A, ) Developer solution (used solution) Potassium hydroxide for IOP Kota/? Potassium sulfite Hirohiro 27 Sodium hydrogen carbonate
7J taboric acid
IO? Diethylene glycol 7.2
0? Ethylenecyagontetraacetic acid /7ri! −
Methylbenzotriazole o, 6ghydroquino7 3ooyl-phenyl-≠+
≠-Dimethyl-3-pyrazolidone +2Of water was added and the pH was adjusted to 0.

lξ-t (B) Developer solution (used solution) Triethylene glycol for 10f +20? j-nitroindazole -! 2 glacial acetic acid
3f nophenyl-3-pyranosidone
/ Yo 2 Add water
, 2JOml part (C) Development g (liquid used) io
Geltaraldehyde for n 2Pt7'
Sodium metabisulfite /2t? After adding water, a starter of the following composition was prepared for 2 J Om.

Starter glacial acetic acid, 270? Add potassium bromide 3 ooy water
Preparation of developer solution: Add part (A) to about Δl of water, 2. -us part (B)
, 2jOml, part (C) rto, gq were sequentially dissolved with stirring, and finally the total amount was made up to 100ml with water.

Next, the entire starter was added at a ratio of 20 to 71 of this working solution.

For fixing, Fuji F (manufactured by Fuji Photo Film (manufactured by 110)) containing the compound of the present invention (Ibara/Kinsho) was used.

For washing, water containing ethyleneaminetetraacetic acid, disodium salt, dihydrate (antifungal agent) o, s9/Ilk was used.

Next, the following development process was carried out using a roller transport type automatic processor as shown in the schematic diagram of FIG.

Processing process Development and fixing Water washing and squeezing Drying temperature +20 Processing time / , 2, 7 seconds IO seconds / 2.7 seconds 72.3 seconds Cloth / After processing (transmission optical a of non-image area with green light) Indicates the value obtained by adding up the dragon.

/ Compound added to fixer (control) (a) (comparative example) (b) (〃) (C) (// ) (1) (present invention) (2) (1/ ) (3) (/ / ) (10) (// ) Addition amount C? /11) 7, ri 0.6 / , 7 / , 7 ha 3 /, r ko, O Residual color after treatment (transmission optical density) O, ri 0, / 67 0, / 4tri0, /guar0, /hiroriO, /≠r (a) Molecular weight /3toriconditions/ Molecular absorption coefficient of the water bath liquid obtained according to the procedure v9. (A,! II nm) 0
(b) Molecular weight Molecular extinction coefficient (t, 2≠n m) of the solution obtained according to the procedure in condition 7 (t, 2≠n m) /, bu × 105 Molecular extinction coefficient (≦, As shown in 2 Hiroguchi m) 0 Mr./, it can be seen that all the fixing solutions containing the compound of the present invention have little residual color after processing.

Similarly, the compounds (1) and (3) of the present invention were added to a developer solution / , 79/l, / , If/(l), respectively, and
When all of the above photosensitive materials are processed, the residual color after processing is 0.
/≠3 and O1/Hirogu.

Example 2 Photographic materials 2Q/~, 207 using the following various sensitizing dyes as sensitizing dyes were carried out in the same manner as IJ/, and were similarly developed using an automatic processor.

In both cases, residual color was reduced when treated with the Kanakura compound fixer of the present invention.

(cH2)4803H-N(C2H5)a Example 3! , anhydro-j13-dichloro-2-ethyl-3,3'-bis(3-sulfopropyl)oxacarbocyanine hydroxide sodium in a 0,3μ cubic silver iodobromide emulsion containing j moles of iodide. Salt (sensitizing dye)
230η/@7 mol, 1 mol of hydrazi/rubber conductor (compound below), 32/1 mol of polyethylene glycol C (molecular weight/000) f300m9/silver/Mo#, and further 1 methylbenztriazole, Hiroshi-Hydroxy -t-methyl-/, J, 3a, 7-chitrazaindene,
Dispersion of polyethylene acrylate, -monohydroxy/,! , j-triazine sodium salt was added. Furthermore,
As a hardening agent, 3-divinylsulfonyl-1-propanol was separated by adjusting the amount so that the swelling percentage was 7.20.

In this way, the coating solution prepared by vA was coated on a polyethylene terephthalate film support, and together with the rζ protective layer, the coating amount of silver was 3.3? /m2, gelatin coating amount (emulsion layer and protective layer) was 3.Of/m2 to obtain a film.

The film of hydrazide/derivatives was exposed to light using an O-ray magenta/cuctoscreen using seven exposure wedges for security screening, and then developed for lAo °C/J seconds with a developer having the following composition. Photographic film ■Fixer G-F/
It was fixed, washed with water, and dried.

The automatic developing machine used here is a pry to dry 6
It is set to 3 seconds.

(Developer composition) Hydroquinone! σ, Og N-methyl-p-aminophenol 0.32≠-methyl-≠-hydroxymethyl-7-phenyl-3-pyrazolidone sodium hydroxide /r, θ potassium diphosphate 3r, θg 3-sulfosalicylic acid ! ! , Of potassium sulfite
/10.0 disodium ethylenediaminetetraacetate /, θ2 potassium bromide io, orj-mefbenzotriazole O9≠2-mercabutobenzimidazole-j-sulfonate 0. jY3-(Omercaptotetrazole) Sodium Hensensulfonate 0.29N-n-
Butyljetanolamine it,ot sodium toluene sulfonate 1.0? Lose all the water
/! pH=//, ≦ (add potassium hydroxide) Use the same water bath solution used in Example/ for the washing water, and replenish the total size (201nchX, 24ffinch) / sheet per sheet, 2JOgo. did.

Similarly, the compound of the present invention (g2
y, 7y/II was added and treated. When the residual color after treatment was determined as K1lii1 in the same manner as in Example,
The remaining color density was o, oto less than the photosensitive material processed without using the compound of the present invention.

Example 4 1 mol of Ag, 4
In the presence of t×70 moles of potassium iridium dichloride (■1) and ammonia, a nitrate water bath solution, potassium iodide, and potassium bromide aqueous solutions were added simultaneously over rg3o minutes, and the pAg of the opening was increased to 7. J'VC maintains a double force average particle size (7
,,2 Jμ, a cubic monodisperse emulsion with a dry silver iodide content of more than 7 mol was prepared. 1 mole of compound f A, g as shown below as a sensitizing dye was added to the silver iodobromide emulsion of Konemono. 10-5 mol of tX was added, and further, as a stabilizer, hydroxyl-O-methyl-#, 3,3a, 7-chitrazaindene, a dispersion of polyethylene acrylate, polyethylene glycol, /, 3-vinylsulfonyl-λ
-propatur, /-phenyl-3-mercaptotetrazole, /, goubis(,?-(4t-acetylamino-pyridinio)propionyloxycutetramethylene dipromide and the same hydrazine derivative as in Example 3 (1 mole of silver) , t×l0-3 mol), adjusted the pH of the film surface to 1J,j with ascorbic acid, and deposited a silver amount of 3.≠?/m on the polyethylene terephthalate film.
2 (the pH of the film surface was measured by the method described in JP-A-6.2-.2j74'j).

). At the same time, a gelatin layer was coated on the emulsion layer so that the total amount of gelatin/coating amount/0 g/m2.

The samples thus prepared were assembled and developed, and their photographic properties were measured.

The developer formulation is as follows.

developer prescription hydroquinone N-methyl-p-aminopheno ole//, disulphate Sodium hydroxide Potassium triphosphate potassium sulfite Ethylenediaminetetravinegar powder Lium salt/trihydrate salt potassium bromide ! -Methylbenzotriazole 3-diethylamino-/l-1 propanediol add water (pH The fixer formulation is as follows.

ammonium thiosulfate sodium sulfite , 33.0? O.

/3.

74t.

Ta　O.

v O? 7.0 ta Meeting, 0? 0, A /　j　　,θ　? ／　　　β //, Otsuj) /l0.0? 30.0? acetic acid Compound (1) of the present invention Add water to 1B 30.09 / , 71 pH=r,o with NaOH.

Development t, to Oc / J seconds Fixation 37°C for 2 seconds Washing 7.2 seconds Dry to Dry A 7 seconds The sample after the above processing had good photographic performance (Dmax, sensitivity) and little residual color. (O9Og3 at Red concentration).

Example 5 0°C, pAg=J'+o, pH=2, average particle size 0, - by double jet method while controlling OK
A silver iodobromide monodisperse cubic emulsion containing 20 μm of silver iodide-00 mol %'r was obtained. A part of this emulsion is used as the whole core,
It was grown as follows. That is, 4 to 0c to the solution containing this core particle and gelatin.

An ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added at pAg, OX pH, O by a double jet method to form a seventh coating layer containing more than 30 moles of silver iodide. Then, an ammoniacal silver nitrate bath solution and a potassium bromide solution were mixed with KpAg = 2, O, pH 2, and Q using the full double jet method to form a J layer of pure silver bromide.
A cubic monodisperse silver iodobromide emulsion with an average grain size of 0°j7 μm was prepared and E-/bound. What is the average silver iodide content of this emulsion? .

The number of θ moles was high.

To E-/, add the following sensitizing dyes A and B=i in the amounts shown below, 10-7 mol of chlorauric acid, 7 x 10-6 mol of sodium thiosulfate, 7 x ammonium thiocyanate.
Calorie 10 moles, perform optimal regular meeting, sulfur sensitization, ≠
-Hydroxy-6-methyl-/, 3.3a, stabilized with 7-chitrazaindenco x 10-2 mol, p, xtf/
The gelatin concentration was fully adjusted so that the amount of gelatin was yy+2 (one side applied).

Furthermore, the following strength-reducing agent was added to the emulsion and the protective film solution, and the hardening agent shown below was further added so that the melting time was 120 minutes.

CH○ HO That is, as an emulsion layer repellency U agent, 7 moles of silver halide 6
t-Butyl-catechol 4L00■, polyvinylpyrrolidone (molecular weight 10.oao) i, oy, styrene/maleic anhydride copolymer,! ? , trimethylolpropane 702, diethylene glycol J? , nitrophenyl-
Triphenyl 7-osphonium chloride 30~, /,
3-di1nitroxybenzene-≠-ammonium sulfonate 2, λ-mercaptobenzimidazole-! -Sulfonic acid powder/1mg, together with the above emulsion, melting time! .

A hardening agent and various additives mentioned below were added to
A silver halide emulsion layer is simultaneously applied on both sides of the polyester film support, which has been subbed using the slide-Hon-Maux method, at the same time as the silver halide emulsion layer, with an amount of /jP/m2 (per side) of the upper 2mm. (Viscosity / / Cp.

Blood supply tension 3 J dyΩ/Tan, coating film thickness! 0 μm), protection # (viscosity 77 cp, i-plane tension 2 j d yn/c
tn% Coating film thickness θ/l m) and coating speed θm
7 m 4 coats coated in multiple layers at the same time, 4 tons of photographic material
Got o7. The amount of silver was 4tj~/dm2 in all cases.

Additionally, the following compounds were added as protective layer additives.

For each 7 g of gelatin, 10 η of /-dimethylol-/=7-romu/-nitromethane, etc. were added.

CH2C00(CH2)9CH3 C1-iCoo(CH2)2CH(CH2)2S Oa
N a mqz A matting agent 7η made of polymethyl methacrylate with an average particle size of 3 μm, a coidal silicone force 709 with an average particle size of 0, 0/j μm, etc. were completely removed.

Each sample had a melting temperature measured using the following method.
The hardener was adjusted so that the time was 10 minutes.

That is, a sample cut to / an X -2 cm was heated at 30°C.
The emulsion layer was immersed in a 1% potassium hydroxide solution for a period of time until the emulsion layer began to bleed out.
It was time.

All measurements of sensitivity and fog were carried out as follows. That is, the specimen is sandwiched between a single optical wedge whose incline is mirror-symmetrically aligned, and exposed to light from both sides simultaneously and equally for 2.3 seconds using a light source with a color temperature of z, +Loo 0.

Follow the steps below and the entire processing time will be shortened! I+ which is seconds
- It was carried out using a sea conveyance type automatic dispersion machine.

Processing vortex Insert processing time - box seconds % image ten days 1) J, t 6CI4t, 1 second landing + crossing 33°C, l-, seconds water washing ten days
Jj C7, 2 seconds squeeze Hiroo6Ct, 7 seconds dry ttJ'c ♂, 1
Total seconds: -4'1.0 seconds Same automatic attack configuration e'', in particular, the following specifications and L7 were used for this attack.

ν In this example, we will use 1 gono and 10 goose pieces, and use silicone rubber (hardness ≠ i degree), a type of ethylene propylene rubber in the processing liquid. E P D M (hardness + i1 degree). General surface roughness of the roller D max = 17 μm1 The number of rollers was one in the developing section, and the total number was J' Hiromoto. The number of opposing rollers was 37. The ratio of the number of rollers in one facing section/total number of rollers is ti7ghiro=0.A/.The amount of developer replenishment is Occ/four cuts, and the amount of fixer replenishment is 4t!c.
The amount of water for washing was 1/min. The air volume of the drying section is 11m/m+n, and the heater capacity is 3KW (
, 200■) was used.

The total processing time is as above ≠ 3 seconds.

The developer was used as the following developer. The following fixer was used as the fixer.

From the obtained characteristic curve, the concentration +/,
The exposure # at O was determined, and the relative sensitivity was determined.

Composition of developer and fixer Developer-7 Fixer-7 10(,) Add enough water to make up to 1 liter.

Next, residual color was evaluated. The transmitted optical density of the non-image area was measured using green light.

Also, for each sample, the above ≠! Second self #! The sensitivity was also determined when the line speed of the J developing machine was reduced to F, (/7.2) and the conventional glue was processed for 0 seconds.
It was shown to.

As is clear from Cloth 3, the sample according to the present invention has overall excellent sensitivity, fogging, residual color, etc., and is suitable for ultra-rapid processing.

In addition, compared to the conventional 0-second processing, it is possible to reduce residual color and reduce the processing time to 2 times, while maintaining high sensitivity compared to the conventional system, which means that the processing capacity is doubled. I know that there is.

Example 6 Complete preparation of a silver halide emulsion consisting of silver chlorobromide (4 mol% average grain size of silver bromide; θ1.2!μ) containing 9/×/θ−5 moles of RJ per mole of silver did.

Anhydro-j, j'- is added to the above emulsion as a sensitizing dye.
Cycloroterethyl-3,3'-di(3-sulfopropyl)oxycarbocyanine hydroxide sodium salt f j Oo mg 71 mol Ag was added.

In addition, 11 hydrokinda is used as a hardening agent.

Sodium t-dichloro-/,J,,t-)riazino and potassium polystyrene sulfonate as a thickener were added and coated onto a polyethylene terephthalate film so that the amount of coated silver was 4tt7m2. A gelatin solution was applied as a protective layer on top of this emulsion layer, with a gelatin amount of 1.
It was applied to a total area of 097m2. As a coating aid for this protective layer, sodium p-dodecylbenzene sulfonate/acid was used, and as a thickener, the same compound as in the emulsion layer was used.

The sample sample thus obtained was exposed through the head wedge using a P-Δ07 printer manufactured by Dainippon Screen Co., Ltd., and then developed using the following developer and fixer formulations.

<Developer> Developer solution LD-1-Jj manufactured by Fuji Photo Film Co., Ltd.

JJ"C,! (1) Second Fixer> Fixer LF3θrK, manufactured by Fuji Photo Film Co., Ltd., containing the coloring agent described in LF3θrK.

<Automatic processor> Compound added to PG-t00fLA fixer manufactured by Fuji Photo Film Co., Ltd. (Control) Invention) (2), (/l') (3) (/7) QO (/7) Table≠ Electricity r1 month [C?/II) 7+ri0. 6/, 7/, 7 no.''/, 1.2, 0 Residual color after processing (transmission optical fl# ship 0, .2/1 0, .2/; 2 θ, / 93 0, / f, 9 θ, / yo l o, 1tt O, / 39 o, it, t When treated with a fixing film containing a total percentage of the compound of the present invention, there was little residual color.

Example 7 Water containing 1N silver nitrate aqueous solution, 0.988 mol of potassium bromide, O, Ol, and 2 mol of potassium iodide J? tj
? A silver iodobromide emulsion was obtained by mixing by the tabulent method while calling 1 for PA and 1 for g to obtain a silver iodobromide emulsion. After washing this emulsion with water and desalting, it was enriched with gold to obtain the optimum sensitivity. The grains of this silver iodobromide emulsion were
14 containing 86% (100) planes with an average particle size of 0.6 μm
It was a face piece.

Weigh out the silver iodobromide emulsion prepared as described above into a 130 g pot, add 2.07xio-' mol of sensitizing dye (+) to 1 mol silver, and surfactant (2)-1 or (2>2). 3
．． Added 54g 1 mol silver and further added 0.02% of 5-mercapto-1-phenylde I Radul. At night, 2% of 2-hydroxy-4,6-cyclotriazine na[-lium salt
At night, add 10% Seratin Gel and water and add 10% each.
In 120g, the amount of silver in this is 3.12g, and the amount of Seratin is 5.
It was prepared in such a way that it weighed 4 g. Separately, prepare an aqueous solution consisting of gelatin as a base, and mix this gelatin solution and a solution containing the emulsion beforehand so that the emulsion is on the support side, and the coating amount of the gelatin solution and the coating amount of the emulsion solution are respectively the same as gelatin I. A photographic effect was obtained by simultaneously coating L7 on polyethylene laminate 7-1 and paper so that the amount was 5 g/rrI and gelatin 225 g/bo.

These samples were exposed to light at a color temperature of 2854 DEG K. and 3200 lux for 1.times.-2 seconds and simulated light exposure for 10@-1 DEG seconds using a xenon lamp.

After exposure, use a developer with the following composition (replenisher amount: 0.39!/
Developed at 35'C for 15 seconds using a photosensitive material) and fixer, stopped, and fixed at 30'C for 12 seconds (replenisher amount: 0.39f).
Fi/n (sensitive material) was carried out and further washed with water to obtain Slips I Lips with a black and white image.

Sensitizing dye (1) Composition of surfactant developer Composition of fixer The absorbance of the remaining sensitizing dye at λma was measured using the unexposed part of this strimbus using a reflectance measurement method using a Hitachi 607 color analyzer. It was measured and used as a scale for evaluating residual color.

The residual color is preferably 0.09 or less as shown in the table, but if it exceeds this value, it will be determined as a residual color by careful observation and it will be difficult to use it as a product. If the value exceeds 01, it is determined as a significant residual color.

The method of the present invention significantly reduces residual color.

In addition, the compound (6) of the present invention was added at 2 x 10-4 mol/emulsion 1.
kg was added to the emulsion layer of the above-mentioned photosensitive material I and subjected to the same treatment, the residual color was as low as 0.058.

Example 8 A sulfur-sensitized silver halide emulsion consisting of 93 mol% silver bromide and 7 mol% silver iodide was prepared. The average diameter of the silver halide grains contained in this emulsion was 0.7 microns. 0.52 mol of silver halide was contained in 1 kg of this emulsion.

Weigh out 1 kg of each emulsion into a bot and add sensitizing dye S.
32 mg/kg of emulsion] was added, and the mixture was mixed and stirred at 40°C. Furthermore, 4-hydroxy-6-methyl 1
．． 3.3a, 7-chitrazaindene at 0. After sequentially adding OIg/1 kg of emulsion, ■-Hydroxy-3,5-dichlorotriazine soda 0.1 g/1 kg of emulsion, 1.0 and 0.1 g of sodium todecylhenzensulfonate/1 kg of emulsion, polyethylene A photographic light-sensitive material was obtained by coating on a terephthalate film base.

Sensitizing dye 5D (C1h) aSOz-(Ctlz) JaThis film sample was measured using a sensitometer with a light source with a color temperature of 285/IK, and a dark red filter (S) manufactured by Fuji Photo Film Co., Ltd. was used as the light source.
C-74) was used for light exposure. After exposure, development was carried out at 20° C. for 3 minutes using a developer having the composition shown below, and after stopping, it was fixed using a fixer shown below, and further washed with water.

Table 8 shows the residual color (transmission optical density of non-image area) after processing.

developer water 50
0 m1N-Methyl-p-aminophenol 2.2g Anhydrous sulfite I.Rium 96.0g Hydroquinone 8.8g Carbonate I~Rium.-
Water salt 56.0g potassium bromide
Add 5.0+x water
1p.

Fixer A compound of the present invention (see table) was added to Fixer L F 308 manufactured by Fuji Photo Film Co., Ltd. in a proportion of 5X]0"' mol/l.

Table 8 In all cases, fixers containing the compound of the present invention had less residual color.

Example 9 A cubic, monodisperse silver chloroiodobromide emulsion (coefficient of variation 0.13, silver iodide 0.1 mol%, silver bromide 33 mol%) with an average grain size of 0°3μ was prepared using the double jet method. Prepared.

After desalting this emulsion in a conventional manner, it was subjected to gold-sulfur sensitization and 6-methyl-4-hydroxy-13,3a,7-
Dye sensitization was carried out by adding citrazaindene and adding 150 mg of the sensitizing dyes shown in Table 9 per mole of silver halide contained in the emulsion.

Potassium bromide 500 mg per mole of silver halide, P-
) Sodium decylhenzenesulfonate 100mg, 5
-Nitroindazole 30 mg, 5-methylhenzo I.
20 mg of Riazole, 1.5 g of styrene/maleic acid copolymer, and 15 g of styrene/butyl acrylate copolymer latex (average particle size 0°/25 μm) were added.

Furthermore, a Te1 herazolium salt compound of the following structural formula is vA1
After adding lXl0-' moles per mole, the amount of coated silver was 4
．． It was coated on a support coated with the subbing described in Example 2 of JP-A-59-19941 so that the amount of gelatin was 0ε/Po and the amount of gelatin was 2.1 g/Po.

At that time, 30 mg/% of 1-decyl-2-(3-isopentyl)succinate-2-sulfonic acid 1-lium was added as a spreading agent so that the gelatin amount was 1.2 g/%.
Samples were prepared by simultaneously applying a protective layer containing 25 mg/n of formalin as a hardening agent. The development conditions were 28°C3 using Konica Fixer CFL851 containing a compound
Processed in 0 seconds.

The hack layer was applied using the following recipe.

[Hack layer prescription] Gelatin 4g/n immatting agent polymethyl methacrylate (particle 11/1 diameter 3.0~4゜Ou) 10mg/rrt latex
Polyethylene acrylate 2g/surfactant)-Dodecylbenzenesulfonic acid mono-lium 40mg/n If fluorine-based surfactant C8F = 7S Oz N CHZ C00KC: 1
I-1゜5 mg/rrT Gelatin Hardener 1, 10 mg/n Dye Mixture of Dye (a), (bL and (c) Dye (a) 50μ/B dye (BL 1.00 mg/B dye) [cl.
50mg/rrr sensitizing dye human], -1 (β-human 1coxyethyl)-3-pheni7
1-5-((3--α-sulfopropyl-α-henzuoxazoliden)-ethylidene]naohydantoin increase) Dye B
'-C(3-sulfopropyl)oxy-S'calfosoanin-1-Roxytos-Lium salt sensitizing dye C
Hydroxy-3-oxapentyl)-3(2-pyridyl)-2-thiodanron-5ylideethylidene)-3
--(N.) Maker Norinyl Butanesulfonate 1 (Maker Dye (a) Dye [bl Dye [cl] Table 9 In both cases, residual color was reduced when treated with a fixer containing the compound of the present invention. .

Example 10 1 剋■■Risui 1f! , 30g of Seratin and 6g of Potassium Bromide in 11g
While stirring, a silver nitrate aqueous solution (5 g as silver nitrate) and a potassium bromide aqueous solution containing 0.1.5 J of potassium iodide were mixed into a container kept at 60°C for 1 minute using the double-scent method. did. Furthermore, silver nitrate aqueous solution (145g as silver nitrate)
) and 1B potassium bromide aqueous solution containing 4.2 g of potassium iodide were added by a double jet method. The addition rate at this time was accelerated so that the flow rate at the end of addition was five times that at the start of addition. After the addition was completed, soluble salts were removed at 35°C by a sedimentation method, the temperature was raised to 40°C, 75 g of gelatin was continuously added, and the pH was adjusted to 67. The resulting emulsion consisted of tabular grains with a projected area diameter of 0.98 μm and an average thickness of 0.138 μm, and a silver iodide content of 3.
It was mol%. This emulsion was chemically sensitized using a combination of gold and sulfur sensitization to prepare an emulsion.

Shashinshi Iman 1 - Gelatin containing sodium polystyrene sulfonate, polymethyl methacrylate fine particles (average particle size 3.0 μm), polyethylene oxide, and a hardening agent in addition to gelatin as a surface protective layer. An aqueous solution was used. 500 mg of the above emulsion sensitizing dye anhydro-55'-nochloro-9-ethyl-33'-di(3-sulfopropyl) oxalocyanine hydrooxide sodium salt
/1 mol Ag and 200 mg/1 mol Ag of potassium iodide were added. Furthermore, as a stabilizer, 4-hydroquine 6-methyl-
1,33a,7-thitrazaindene and 2,6-bis(hydroxyamino)-4diethylamine-1,35-i liazine, trimebrolpropane as a drying antifoggant, coating aid, and hardening agent were added. A photographic material was prepared by coating the solution as a liquid and drying it simultaneously with a surface protective layer on both sides of a polyethylene terephthalate support. The amount of coated silver on both sides of the photographic material was 3.7 g/rl.

Processing method The developer and fixer (1) formulations are as follows.

Chew 1 ethylenetriaminepentaacetic acid 2g 1-phenyl-3-pyrazolidone 2g hydroquinone 30g 5-nitroindazole (1,25g 5-methylhencytriazole 002g potassium bromide)
1g anhydrous sulfite I.lium
60g potassium hydroxide 30
g Potassium carbonate 5 g Boric acid 6 g Diethylene glycol 20 g Glutaraldehyde
Add 5g of water to bring the total volume to 1ρ (p I-1 was adjusted to 1.0.50.) Constant 1 liquid -
+L-mo Ammonium thiosulfate 175g Sodium silicate (anhydrous) 20.0g Boric acid
8.0g Ethylenediaminetetraacetic acid disodium dihydrate 0.1g Aluminum sulfate 1.5. Og value acid
2.0g glacial acetic acid
Calorie 22.0g water
1.02 (pH is adjusted to 4.20.) Processing process The above-mentioned replenisher 1! is placed in the tank of the automatic processor as a developer. A solution to which 20 g of an aqueous solution (starter) containing 2 g of potassium bromide and 4 g of acetic acid (90%) was added was used, and the replenisher was replenished at a constant rate each time the sensitive material was processed thereafter. A fixing solution with the same composition as the replenisher was used in the developing machine's tank.

The residual color caused by the sensitizing dye in the processing solution when 500 sheets of each of the above bad phases were processed with a cut-out size under various conditions as follows (
500th sheet) is as follows.

1, 2 1 Example 11 A color photosensitive material 1.101 having the same structure as Sample 01 of Example I of JP-A-2665/1.0 was prepared.

Sample 1101 was cut and folded to a width of 35 mm, exposed to standard light in a camera, and mixed with 1M of each sample using an automatic processor as described below. This was continued for 10 minutes.

The magenta transmission density of the unexposed area of each test card processed at the beginning (fresh processing) and the end (running processing) of processing was measured using an X-Rye 1310 model Graphink densitometer. The value of ()I/run process), that is, the change in magenta density due to running, was determined.

Additionally, each sample in the running process was heated to 60'C1 relative humidity 7.
The samples were stored under 0% conditions for one week, and changes in magenta transmission density during this period were evaluated.

The above results are listed in Table-11.

Color development 2 minutes OO seconds 38°C 390mR bleaching
White 45 seconds 38°C 270ml Bleach fixing 1 minute 30 seconds 38°C: 530ml 121
0β P Water washing (2) 1.5 seconds 35°C1210d
4j2 Stable 15 seconds 38°C210mβ
4! Drying 1 minute 15 seconds After the photosensitive material is immersed in the color developer at 55°C or higher,
The wet processing time until the stabilizing solution is removed is 5 minutes OO seconds. Also, the total amount of replenishment is 1730m! It is.

(Color developer) Mother solution (g) Replenisher (g) Diethylene[-liaminepentaacetic acid 1-hydroxylycylidene-11-diphosboxylic acid, 0 1.1 3.2 Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxolamine sulfate 4-(N-ethyl-N β-human 1koxyethylamino)-2 Methylaniline sulfate 45 Add water (
(Tap water) 4 30,0 1,4 1,5 mg 5.8 37.0 3.5 7.2 1.01 10.20 ■ 2 [; Bleach accelerator 0.010 mol ammonia water (27%) 5, Oml water Plus (tap water) 1.0! pH5
, 3 (Bleach-fix solution) Common to mother liquor and replenisher (unit: g) Ethylenediaminetetraacetic acid ferric ammonium trihydrate 80.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Ammonium sulfite, rum 15.0 Ammonium thiosulfate aqueous solution (700 g /j2) 300. 0ml
Ammonia water (27%) 6.0m11
Compound of the invention (see table) 2.0 Add water 1.01 pH 7
, 2 (Water solution) All mother solution replenisher common tap water was mixed with H-type strongly acidic cation exchange resin (Amberly 1-IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberly IR-120B manufactured by Rohm and Haas). Water was passed through a mixed bed column packed with 400) to give the following water quality.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (3
7%) 1.0mρ polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add 0.3 ethylenediaminetetraacetic acid disodium salt solution (tap water) T) H 0,05 1,0I2 5, O -8,0 Table 11 As shown in Table 11, according to the present invention, the increase in magenta density in the unexposed area due to running can be suppressed to a level that does not cause any actual damage. At the same time, it was also possible to suppress the appearance of magenta density in the unexposed areas under high temperature and high temperature storage. Furthermore, it has been found that the following effects can be further improved by reducing the thickness of the photographic constituent layer and increasing the swelling rate T%.

Example 12 A multilayer color photosensitive film J201 was prepared by coating each layer having the composition shown below on a subbed cellulose triacetate film support.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rl (units). For silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount in the same layer The coating amount per mole of silver halide is shown in mole units.

1st layer (antihalation layer) Black colloidal silver 0. 2 gelatin
1.2 Ultraviolet absorber UV-10
,05 Same UV-20,1 Same UV-30,1 Dispersion oil 0IL-10,02 Second layer (intermediate layer) Fine grain silver bromide (average grain size 0.07μ) Gelatin third layer (first red-sensitive emulsion) Eyebrows) Monodispersed emulsion (silver iodide 6 mol%, μm coefficient of variation 15%) Gelatin sensitizing dye A Sensitizing dye B Sensitizing dye C cp-b cp-c cp-d B5-1 B5-2 4th layer (Intermediate layer) Gelatin 0, 15 1.2 Average particle size 0.4 1.42 1, 1 2.0×10-'1.0X10''-'0.3X10-' 0.35 0.052 0.047 0.023 0.035 0.10 0.10 1, 0 C1)-+) 0.10H
BS-10,05 5th layer (second red-sensitive emulsion layer) Monodispersed emulsion (silver iodide 6 mol%, average grain size 0.5 μm variation coefficient x 5%) L, 38 gelatin
1. 2 Sensitizing dye A
1.5X10-' sensitizing dye B
2.0xlO-' sensitizing dye CO, 5xlO-' cp-bo, 150Cp-
d, 0.027D-10,
005 D-20,010 HBS-10,050 HBS-20,060 6th layer (third red-sensitive emulsion layer) Monodispersed emulsion (silver iodide 7 mol%, average grain size 1.1 μm, coefficient of variation 16%) 2 .08 gelatin
1.7Cp-ao, 060 cp-c cp-a B5-1 7th layer (middle layer) Gelatin 0.038 0.006 0.012 1.2 Cpd-A o,
05HBS-20,05 8th layer (first green sensitive layer) Monodisperse silver iodobromide emulsion (silver iodide 3 mol%, average grain size 0.4
μm, coefficient of variation 19%) 0.64 monodisperse silver iodobromide emulsion (
Silver iodide 6 mol%, average grain size 0.1 μm, coefficient of variation 18%
) 1.12 gelatin 1,2 sensitizing dye D lXl0-' sensitizing dye E 4xto'' sensitizing dye F
lXl0-'cp-h,
0.20cp-f
o, 61cl)-g
0.084Cp-k
O,035Cp-10,036 D-30,041 D-40,018 HBS-10,25 HBS-20,45 9th layer (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 7 Mol%, average particle size 1.0
μm, coefficient of variation 18%) 2.07 gelatin
1.7 sensitizing dye D
1. 5XlO sensitizing dye E 2.3
X10 sensitizing dye F 1. 5XlO
Cp-fo, 007 cp-h, 0.012Cp
-g O,009HBS-2
0,088 10th layer (middle layer) Yellow colloidal silver 0.06 gelatin
1.4Cpd-A
0. 3HBS-10,3 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.4
μm1 coefficient of variation 20%) 0.31 monodisperse silver iodobromide emulsion (
Silver iodide 5 mol%, average grain size 0.9 μm, coefficient of variation 17%
) 0.38 Gelatin 2.0 Sensitizing dye G lXl0-' Sensitizing dye HlXl0-' Cp-i0゜63 Cp-jo, 57 D-10,020 D-40,015 HBS-10,05 12th layer ( 2nd blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 8 mol%, average grain size 1.3
μm, coefficient of variation 18%) 0.77 gelatin
0.7 sensitizing dye G
5X10-'' Sensitizing dye H5X10-' Cp-io, 10 Cp-jo, i.

D-40,005 HBS-20,10 13th layer (middle layer) Gelatin 0.7Cp-mO,
l UV-10, l UV-20, l UV-30, L HBS-10,05 HBS-20,05 Notification 14 (Protective layer) Monodispersed silver iodobromide emulsion (silver iodide 4 mol%, average grain Diameter 0.0
5 μm, coefficient of variation 10%) 0.1 gelatin 1.5 polymethyl methacrylate particles (average 1.5 μm) −1.1 l was added to other surfactants.

0.1 0.2 0.2 Gelatin hardening agent H- Same D (CH2)4SO,.

(CH2)4so3Na 2L (CH2)3SO, - (CH2:hSO3e (CH2)jSOJa Same G (CH2)zsOsNa Same H (CH2)3SO3e (CH2)3sO3Na H H IL-1 p-a Song 0CH1lCH2CONHCH2CH20CH- p H H H H p-c H C, H, □ (1) p 0■ Cp f Cp Cp-k Cp-β j2 BS ni-1 ■ 2H5 H-1 Same as above UV V Compound CpdA H J Shi13 CH2=CH-3Q2- CH2 CH2=CH-3Q, -CH2 Reduce the amount of gelatin and hardener in sample 1201 above,
The following samples were prepared in total.

Sample Thickness of photographic constituent layer Film swelling rate TVz1201
24μ 12 seconds 1202
' 19μ 8 seconds 1203 1
After exposing the above samples to light in the camera for 6μ for 6 seconds, each sample was mixed at 1% per day in the same manner as in Example 11, and continued for a total of 10 days.

The processing carried out is as follows.

Sample processing and evaluation were performed in the same manner as in Example-11.

H 14' color development bleaching fixing processing time 1 minute 30 seconds 30 seconds 1 minute 15 seconds Processing temperature 37.8°C 37.8°C 37.8°C Replenishment amount 50d 30m1 00d Tank capacity Drying 1 Minutes 00 seconds 55.0°C The replenishment amount is 4 minutes for wet processing over 1m, the total replenishment amount is 1330
ml.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 6.0 Potassium carbonate
30.0 37.0 Potassium bromide
1.3 Potassium iodide 1.2 mg Hydroxylamine sulfate 4-(N-ethyl-N β-hydroxyethylamino)-2 Add methylaniline sulfate and H (bleach solution) 2.0 3.8 4.7 7.5 1, OA 1.0f1 10.00 10.20 Mother liquor (g) Replenisher (g) ■, 3-Diaminopropane tetraacetic acid ferric salt Ethylenediaminetetraacetic acid Ammonium bromide Ammonium nitrate Ammonia water (27%) Acetic acid (98%) 4.0 5.0 160, 0 30.0 20, FW 23.0d 80.0d 120.0TLl Compound of the present invention (see table) 2.0 Add water 1.0! pH4.3 (Fixer) 2.0 1.0ρ 4.0 Mother liquor (g) Replenisher (g) Ethylenediamine tetrahedral vinegar dichloride salt 0.5 0.7 Ammonium sulfite 15.0 25.0 Bisulfite Thorium 5.0 10.0 Ammonium thiosulfate aqueous solution (700g/IV,) 270.0m
E Add 320.0ml water
1. , Off 1.0ffpl (6,76,6 (stable liquid) Mother liquor, replenisher common (unit: g) Tap water
1,0βho/l/ Marine (37
%) 1.2ml 5-chloro-2-methyl-4-isothiazolin-3-one 2-methyl-4-isothiazo 9mg Similar to Example 11, the present invention suppresses the increase in magenta density in the unexposed area. It is also effective in preventing northward rise in cyan concentration in unexposed areas under high temperature storage.

Example 13 Sample 10 of Example 1 of JP-A No. 1,77547
Color photographic paper with the same configuration as I was produced.

The sample was subjected to continuous processing (running test) using a paper processor until the tank capacity for color development was replenished twice as much in the next processing step.

For science and engineering use, consistency - 1st punishment - replenishment - release "FureG-rich color development" 38°C 20 seconds 161mu
171° bleach fixing 35-38°C 20 seconds 215mff
1.7 (2 rinses ■ 35-38'C7 seconds
-10ff rinse■ 35~38”C7 seconds -10
2 rinse■ 35-38'C6 seconds 350m1 10
E Drying 70 to 80°C for 30 seconds *Replenishment amount is per 1% of the photosensitive material (Rinse tank countercurrent flow from ■ to ■9) The composition of each processing solution is as follows.

Phosphorus 3-one surfactant CC,,H2,-0-(CH2CH.

ethylene glycol The results are shown in Table-12.

Table 12 0>- Om) H Kazutomo: Old [Water ethylenediamine-N Methanesulfonamidoethyl]-3 Methyl-4-aminoaniline sulfate N,N-bis(carboxymethyl)hydra,, LLL side - charging 800 mfl 800 mn 1.5g O,Ol, 5g 8.0g 1 .4g 5g 5.0g 2.0.; 12.0g 25+g 7.0g Add water and pl-1 (25°C) 1000mff 1000mQ 10.05 10.45 In Yodo ftJ, (tank fluid and replenishment fluid are the same )water
400ml
l Ammonium thiosulfate (70%) 1.00 ml
1 Sodium sulfite 17g Iron (+11) ammonium ethylenediaminetetraacetate 55g Disodium ethylenecyaminetetraacetate 5g Compound of the invention f2) 2 One embodiment of the machine system is shown.

1: Developing tank 2 - Fixing tank 3: Washing tank 4: Water (water) - Ivy tank 5: Developer concentrate stop Ivy tank 6: Fixer concentrate I - Ivy tank 7: Squeeze roller cleaning tank P: Add pump water I 000 m1p
H (25°C) 6.0% (tank fluid and refill fluid are the same) Ion exchange water (3 pp each of calcium and magnesium
m or less) When treated with a processing solution containing the compound of the present invention obtained as described above, the reflection density based on the residual color of the sensitizing dye in the unexposed area is 0 compared to a processing solution that does not contain the compound of the present invention. .050
significantly improved.

Claims (4)

[Claims] (1) A processing solution for silver halide photosensitive materials containing at least one tri- or tetracyclic heterocyclic compound or a salt thereof that can be adsorbed on silver halide. (2) The processing liquid according to claim 1, wherein the processing liquid is a liquid having fixing ability. (3) A silver halide photosensitive material that satisfies Condition 1 below and contains at least one tri- or tetracyclic heterocyclic compound or a salt thereof that can be adsorbed to silver halide. Condition 1: Anhydro-5,5'-dichloro-9-ethyl-3,3
'-Bis(3-sulfopropyl)thiacarbocyanine hydroxide pyridinium salt 4.0×10^-^4 mol/l aqueous solution 2ml and potassium chloride 1.0×10^-^
1 ml of a 1 mol/l aqueous solution and 4 ml of an 8.0×10^-^2 mol/l aqueous solution of the compound were added to this mixture, and the mixture was diluted with water to a constant volume of 10 ml. The molecular extinction coefficient of this aqueous solution at 624 nm is 1.0.
×10^5 or less. (4) Processing the exposed silver halide photosensitive material in the presence of at least one tri- or tetracyclic heterocyclic compound or its salt that satisfies the following condition 1 and can be adsorbed to silver halide. A method for processing a silver halide photosensitive material, characterized by: Condition 1: Anhydro-5,5'-dichloro-9-ethyl-3,3
'-Bis(3-sulfopropyl)thiacarbocyanine hydroxide pyridinium salt 4.0×10^-^4 mol/l aqueous solution 2ml and potassium chloride 1.0×10^-^
1 ml of a 1 mol/l aqueous solution and 4 ml of an 8.0×10^-^2 mol/l aqueous solution of the compound were added to this mixture, and the mixture was diluted with water to a constant volume of 10 ml. The molecular extinction coefficient of this aqueous solution at 624 nm is 1.0.
×10^5 or less.